Flotation of ores



Patented Nov. 7, 1944 UNITED sTArEs PATENT OFFICE FLOTATION OF ORES Frank J. Ca'hn, Chicago, 111., assignor to The Emulsol Corporation, Chicago, Ill.

No Drawing. Application July 3, 1941,

- Serial No. 400,910

. sulphide ores, in connection with which the results thus far obtained leave much to be desired, not only from the standpoint of operative efficiency but also with respect to reagent cost.

One of the objects of my present invention is to overcome various of the disadvantages which 27 Claims. (Cl. 209-166) -mo'nium compounds, representative examples of have heretofore attended separation or flotation processes, particularly as regards the treatment of certain classes of ores.

Another object of my invention is the provision of novel flotation reagent compositions.

Another, and particularly important, object of my invention is concerned with separation processes, and especially froth flotation processes, for separating silica and siliceous materials from ores containing the same.

Other objects and features of the invention will become apparent as the description proceeds.

The separation of the valuable or desired constituents from the undesired gangue in various types of ores by means of cationic agents has heretofore been suggested. Among the patents which disclose the use of cationic agents'in ore separation processes are, for example, the following: 2,088,325; 2,120,217; 2,132,902; 2,161,011; 2,168,849; 2,173,909; 2,177,985; 2,185,224; 2,185,- 968; 2,195,724; 2,205,503; 2,205,923; 2,221,485; 2,222,728; and 2,238,439.

Among the cationic flotation agents disclosed in the aforementioned patents are salts of normal,

primary, aliphatic amines having at least 6, usually from 6 to 18, and preferably from 8' to 14, carbon atoms, representative examples of which are the hydrochlorides, hydrobromides, nitrates, and acetates of hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine or laurylamine, tetradecylamine,

' hexadecylamine, octadecylamine, and the like.

Patent No. 2,168,849, above mentioned, discloses higher molecular weight secondary amines and salts thereof, such as dioctyl amine hydrochloride and acetate.

Patent No. 2,132,902, also listed hereinabove, discloses the froth flotation of negatively charged minerals, particularly non-sulphide ores, wherein which are dodecyl pyridinium bromide and iodide, cetyl pyridinium bromide and the like. Dodecylamine hydrochloride, hexadecylamine hydrochloride, and heptadecylamine hydrochloride are also disclosed as examples of flotation agents havin a positively charged surface active ion.

I have discovered that concentration or flotation practices, such as are described in the foregoing patents, or, in general, any process where a cationic agent is employed as a flotation agent, may be markedly improved if the flotation or separation treatment is carried out in the presence of certain substances. The improvements manifest themselves either in greater recovery of desired mineral values or substantial economy in reagent cost or consumption, and in at least most cases both advantages accrue. The substances which,-when used in conjunction with the cationic flotation agents, accomplish the highly unexpected and unusual results in accordance with the present invention may be characterized as certain so-called non-ionic substances.

These non-ionic addition substances comprise the aliphatic (including cycloaliphatic) carboxylic acid, particularly faty acid, partial esters of aliphatic polyhydroxy substances, the aliphatic carboxylic acid radical containing from 6 to 10 carbon atoms, and preferably from '7 to 9 carbon atoms. Particularly satisfactory are the caprylic and pelargonic acid mono-esters of glycerin and diethylene glycol. Others 01' the substances of this group are the caproic, enanthic, naphth'enic, 1

caprylic, pelargonic, and caprlc acid partial esters, particularly the mono-esters, of such aliphatic polyhydroxy substances as glycerin, ethylene glycol, propylene glycol, trimethylene glycol; polyethylene glycols such as diethylene glycol and triethylene glycol; polyglycerols such as-diglycerol, triglycerol, tetraglycerol and the like including mixtures thereof; carbohydrates, sugars and sugar alcohols such as dextrose, sucrose, xylose, arabinose, fructose, maltose, dextrins, starches, arabitol, mannitol, sorbitol, dulcitcl, mannitan, sorbitan, and the like.

The non-ionic agent which is used together with the cationic flotation agents utilized inaccordance with the present invention, as, for example, the higher amine hydrochlorides or the quaternary ammonium derivatives, gives the best rethe frothing is carried out in the presence of an organic compound, the surface active portion of which is a positive ion. The preferred compounds disclosed in said patent are quaternary am.-

suits, in general, where the non-ionic or cationic addition agent contains a straight chain aliphatic or fatty chain of from 6 to 10 carbon atoms, in the usual case preferably 8 carbon atoms, and the higher amine hydrochloride or the quaternary ammonium derivative, as the case may be, contains a straight chain aliphatic or fatty chain of from 12 to 18 carbon atoms, particularly 12 to 14 carbon atoms. While the proportions may be varied, the best results are, in general, obtained where the non-ionic or cationic addition agent is utilized in amounts substantially less than the amount of the higher amine hydrochloride or similar cationic flotation agents which are used in accordance with the present invention.

It will be understood, of course, that the various flotation compositions, falling within the scope of the invention, will vary in their emcacy and this variation will also occur with respect to different ores which may be separated by the use thereof. In this same general connection, it will be understood that the optimum proportions of flotation agents, or compositions containing the same, will also be variable although, as a rule,

- amounts of the order of a few pounds per ton of ore will be utilized. Those skilled in the art will, in the light of my teachings, readily be able to adapt my invention to the treatment of particular ores.

- The following examples are illustrative of the practice of my invention as applied to the flotation of a manganese ore (pyrolusite) the socalled Three Kids ore. It will be understood that the examples are not to be construed as being in any way limitative of the scope of my invention. Thus, for example, various changes may be made with respect to reagent choice, proportions of reagents, selection of particular ores and the like which will be clear to those versed in the art in the light of the guiding principles disclosed herein.

Exulrtss About 500 grams of manganese ore, ground to -100 +200 mesh, are suspended in 3 liters of tap water. The suspension is stirred mechanically and aerated. The reagent is added in stages and after each addition the frothis c ol1ected until it is free of suspended solids. Each froth is collected separately and the suspended matter therein is weighed and analyzed for manganese. It will be understood that the silica is floated and the manganese concentrate remains in the cell. a

The reagent consumption, lb./T, is the amount of reagent necessary, in pounds per ton of ore, to produce a concentrate containing 43.7% manganese from an original head containing about 32% manganese. The percent recovery is the percentage of manganese in the 43.7 manganese concentrate based on all of the manganese introduced into the flotation cell.

In the following tables, reagent A will be used to identify the higher fatty acid ester of monoethanolamine hydrochloride, a cationic flotation reagent prepared as described in my copending application, Serial No. 390,110, flled April 24, 1941, of which the present application is a continuation-in-part, the higher fatty acid being obtained by distilling 100 parts of mixed coconut oil fatty acids and utilizing the first 80 parts which come. of! in the distillation.

iii

aseaesa In Table II, reagent B is a cationic flotation agent comprising the ester of monoethanolamine hydrochloride prepared from what may be characterized as whole coconut oil mixed fatty acids. that is, the mixed fatty acids obtained from coconut oil without distilling oi! any fraction of said fatty acids.

' Table II Reagent R Per cent Reagent (parts by weight) used Mn in um head Reagent B 6. 7 70. 6 33. 3 8 parts reagent 8+2 parts caprylic acid mono-ester oi diethylene glycoh. 2. 9 72. 5 M. 3

Table III Reagent R Per cent Reagent (parts by weight) used emvery' Mn in 11:41 W head Substantially pure lauryl amine hydrochloride 2. 55 75. 0 32. 2 9 parts substantially pure lauryl amino hydrochloride-H part cam-Kilo acid mono-ester oi triet ylcnc glycol 2 0 8i. 7 31. 0

As indicated hereinabove, the invention is especially useful in connection with the separation of silica and siliceous materials from various ores. It is, however, also highly useful for the separation of the valuable constituents from the gangue materials in ores or mineral mixtures of various types. Illustrative examples of ores which may be treated with satisfactory results in accordance with the teachings of my present invention are, among others, phosphates, such as are present in the non-metallic minerah of the type found in Florida, Tennessee, Idaho, and Montana, feldspars, ilmenite ores, pyroxenes, spinels, picotite, magnetite, niicas such as biotite and muscovite. It is preferable, particularly with the phosphate ores, initially to deslime them prior to carrying out the flotation separation treatment, such prochloride and potassium chloride may be separated from each other in a saturated brine made from an ore containing the same, such as sylvinite.

It will also be understood that my novel flotation agents or flotation compositions may be utilized together with one or more already known agents such as collecting agents, frothing agents, depressing agents, emulsifying agents, dispersing agents, activating agents, deactivating agents, inhibitors, in general, organic and inorganic conditioning agents, and the like. These include, among others, mineral and vegetable oils, fuel oil, kerosene, mercaptans, xanthates, organic sulphides, hydrosuiphides, carbamates, thio-carbamates, thio-ureas, di-thio-ureas, azo and diazo compounds, higher molecular weight alkyl sulphates such as octyl sulphate, iauryl sulphate, oleyl sulphate, cetyl sulphate, stearyl sulphate, said higher alkyi sulphates being used preferably in the form of their salts such as sodium and the like; alkali metal and heavy metal soaps, higher aQs'easss sulphonated oils and sulphonated higher fatty acids such as Turkey red oil and sulphonated oleic acid; gelatin, glue, starch, copper sulphate and other salts of copper, mercury and lead: alkali metal sulphides and fluorides, such as sodium sulphide and sodium fluoride; alkali metal silicates such as sodium silicates; acids such as sulphuric acid, hydrochloric acid and the like; salts such as potassium ferro-cyanide and other agents which are commonly employed .in flotation and agglomeration processes.

The term "higher," as used herein and in the claims to describe carboxylic and fatty acids and the like, will be understood to mean at least eight carbon atoms unless otherwise specifically stated.

While the invention has been described in detail, it is to be understood that the scope thereof is not to be limited other than is set forth in the claims.

What I claim as new and desire to protect by Letters Patent of the United States is:

1. In a flotation process for the concentration of ores, wherein at least one of the flotation agents employed comprises a cationic agent, the step which comprises conducting the flotation operation in the presence of an aliphatic polyhydroxy substance partially esterifled with an aliphatic carboxylic acid containing from 6 to 10 carbon atoms.

2. In a froth flotation process for the concentration of ores, wherein at least one of the flotation agents employed comprises a cationic agent, the step which comprises conducting the flotation operation in the presence of a mono-ester'of an aliphatic polyhydroxy substance with an aliphatic carboxylic acid containing from 6 to 10 carbon atoms.

3. In a froth flotation process for the concentration of ores, wherein at least one of the flotation agents employed comprises a nitrogenous cationic collecting agent, the step which comprises conducting the flotation operation in the presence of a caprylic acid mono-ester of an aliphatic polyhydroxy substance. 1

4. A flotation process for the concentration of ores, which comprises carrying out the concentration .in the presence of an aqueous medium containing relatively small proportions of a cationic collector and a mono-ester of an aliphatic polyhydroxy substance with an aliphatic carboxylic acid containing from 7 to 9 carbon atoms, said aliphatic polyhydroxy substance being selected from the group consisting of glycerin and glycols.

5. A froth flotation process for the concentration of ores, which comprises frothing the ore in the presence of an aqueous medium containing relatively small proportions of a cationic collector and an aliphatic polyhydroxy substance partially esterifled with an aliphatic carboxylic acid containing from 6 to 10 carbon atoms, said aliphatic polyhydroxy substance being selected from the group consisting of glycerin and gylcols.

6. A froth flotation process for the concentration of ores, which comprises frothing the ore in the presence of an aqueous medium containing relatively small proportions of a cationic collector and a caprylic acid mono-ester of an aliphatic polyhydroxy substance selected from the group consisting of glycerin and glycols.

7. A froth flotation process for the separation s of silica or siliceous materials from mineral values present in said ores which comprises frothing the ores in the presence of an aqueous medium containing relatively small proportions of a water-soluble salt of an aliphatic amine contain-- ing from 6 to 18 carbon atoms, and a mono-ester of an aliphatic polyhydroxy substance with a fatty acid containingfrom 6 to 10 carbon atoms. 8. A flotation process for the separation of silica or siliceous materials from mineral values present in said ores which comprises eflecting the separation in the presence of an aqueous medium containing relatively small proportions of a water-soluble salt of an aliphatic amine containing from 6 to 18 carbon atoms, and an aliphatic polyhydroxy substance partially esterifled with a fatty acid containing from 7 to 9 carbon atoms.

9. A froth flotation process for the separation of silica or siliceous materials from mineral values present in said ores which comprises frothing the ores in the presence of an aqueous medium containing relatively small proportions of a water-soluble salt of an aliphatic straight chain primary amine containing from 8 to 14 carbon atoms, and a caprylic acid mono-ester of an aliphatic polyhydroxy substance.

10. A froth flotation process for the separation of potassium chloride from an aqueous pulp containing the same which comprises frothing the pulp in the presence of relatively small proportions of a water-soluble salt of a normal, primary aliphatic amine containing at least 6 carbon atoms in the aliphatic chain, and a monoester of an aliphatic polyhydroxy substance with a fatty acid containing from 6 to 10 carbon atoms.

11. A froth flotation Process for the separation of silica or siliceous materials from mineral values present in ores which comprises frothing the ores in the presence of an aqueous medium containing relatively small proportions oi lauryl amine hydrochloride and a mono-ester of an allphatic polyhydroxy substance with a fatty acid,

ing a siliceous gangue which comprises frothing the ore in the presence of an aqueous medium containing a higher molecular weight amine hydrochloride cationic collector and an aliphatic polyhydroxy substance partially esterifled with an aliphatic carboxylic acid containing from 6 to 10 carbon atoms.

14. A froth flotation process for the concentration of ores selected from the group consisting of manganese and magnesium ores containing a siliceous gangue which comprises frothing the ore in the presence of an aqueous medium containing a nitrogenous cationic substance and a monoester of an aliphatic polyhydroxy substance with an aliphatic carboxylic acid containing from 6 to 10 carbon atoms.

15. A froth flotation process for the separation of silica or siliceous materials from mineral values present in ores which comprises frothing the ores in the presence of an aqueous medium containing relatively small proportions of the hydrochloride of an aliphatic amine having from 6 to 18 carbon atoms, and an aliphatic polyhydroxy substance partially estei'ifled with a fatty .acid containing from 7 to 9 carbon atoms.

16. A froth flotation process for the concentration of ores selected from the group consisting of manganese and magnesium ores containing a siliceous gangue which comprises frothing the ore in the presence of an aqueous medium containing lauryl amine hydrochloride and a caprylic acid mono-ester of an aliphatic polyhydroxy substance selected from the group consisting of glycerin and glycols.

17. A process of separating ores by froth flotation which includes subjecting a pulp of the ore to froth flotation in the presence of a nitrogenous cationic substance in the form of an aliphatic derivative, the aliphatic chain of which contains from 6 to 18 carbon atoms, and a small proportion of a mono-ester of an aliphatic polyhydroxy substance with an aliphatic carboxylic acid containing from 7 to 9 carbon atoms.

18. A process of separating ores by froth flotation which includes subiecting a pulp of the ore to froth flotation in the presence of a nitrogenous cationic substance iin the form of an allphatic derivative, the aliphatic chain of which contains from 6 to 18 carbon atoms, and a small proportion of an aliphatic polyhydroxy substance partially esterifled with an aliphatic carboxylic acid containing from 6 to 10 carbon atoms.

19. A process of separating ores by froth flotation which includes subjecting a pulp of the ore to froth flotation in the presence of a nitrogenous cationic substance in the form of an aliphatic straight chain derivative, the aliphatic chain of which contains from 6 to 18 carbon atoms, and a small proportion of a caprylic acid mono-ester of an aliphatic polyhydroxy substance selected from the group consisting of glycerin and glycols.

20. A froth flotation process for the separation of potassium chloride from a mixture of potassium chloride, sodium chloride, and other impurities which comprises frothing a pulp of said mixture in its saturated brine in the presence of an aqueous medium containing relatively small proportions of lauryl amine hydrochloride and a caprylic acid mono-ester of an aliphatic polyhydroxy substance selected from the group consisting of glycerin and glycols.

21. A process for the froth flotation of negatively charged non-sulphide ores which comassess:

prises frothing an aqueous suspension of said ores in the presence of small proportions of an organic compound, the surface active portion of which is a positive ion, and a mono-ester of an aliphatic polyhydroxy substance with an aliphatic carboxylic acid containing from 6 to 10 carbon atoms.

22. A process for the froth flotation of negatively charged minerals which comprises frothing an aqueous suspension of ore containing said minerals in the presence oi. small proportions of a quaternary ammonium compound having a hydrocarbon radical of from 8' to 18 carbon atoms, and a caprylic acid mono-ester of an aliphatic polyhydroxy substance.

23. A process for the froth flotation of negatively charged non-sulphide ores which comprises frothing an aqueous suspension of said ores in the presence of small proportions. of an organic compound, the surface active portion of which is a positive ion, and a mono-ester of an aliphatic polyhydroxy substance with an aliphatic carboxylic acid containing from 6 to 10 carbon atoms.

24. A process for the froth flotation of negatively charged non-sulphide ores which comprises frothing an aqueous suspension of said ores in the presence of small proportions of an organic nitrogenous compound, the surface active portion of which is a positive ion, and a mono-ester of an aliphatic polyhydroxy substance with a fatty acid containing from 6 to 10 carbon atoms.

25. A flotation agent comprising a mixture of a cationic collector in the form of hydrochlorides of a mixture of aliphatic amines containing from 6 to 18 carbon atoms, and an aliphatic carboxylic acid mono-ester of an aliphatic polyhydroxy substance, said aliphatic carboxylic acid containing from 6 to 10 carbon atoms.

26. A flotation agent comprising a mixture of lauryl amine hydrochloride and a mono-ester of an aliphatic polyhydroxy substance with an aliphatic carboxylic acid containing from 6 to 10 carbonatoms.

27. A flotation agent comprising a mixture of lauryl amine hydrochloride and a caprylic' acid mono-ester of an aliphatic polyhydroxy substance selected from the group consisting of glycerin and glycols.

FRANK J. CAI-IN. 

